A composite receptor method applied to Philadelphia aerosol


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Environ. Sci. Technol. 1988, 22, 46-52

Glass, G. E.; Loucks, 0. L. Environ. Sci. Technol. 1985, 20(1), 35-43. Bowersox, V. C.; De Pena, R. G. J.Geophys. Res. C: Oceans Atmos. 1980,85(ClO), 5614-5620. Summers, P. W.; Bowersox, V. C.; Stensland,G. J. Water, Air, Soil Pollut. 1986, 31, 523-535. Lindberg, S. E. Atmos. Environ. 1982, 16(7),1701-1709.

(47) Clark,G. B.; Lawrence, M. B. Mariners Weather Log 1985, 29(1), 1-7.

Received for review March 30,1987. Revised manuscript received August 4, 1987. Accepted September 9, 1987. This work was supported in part by NSF Grant ATM-8512537.

A Composite Receptor Method Applied to Philadelphia Aerosol Thomas G. Dzubay" and Robert K. Stevens Atmospheric Sclences Research Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina 2771 1

Glen E. Gordon, Ilhan Olmez,+and Ann E. Sheffleld Department of Chemistry and Biochemistry, Universlty of Maryland, College Park, Maryland 20742

Willlam J. Courtney$ Northrop Services Inc., Research Triangle Park, North Carolina 27709

A composite of chemical mass balances, multiple linear regression, and wind trajectory receptor models was developed to apportion particulate mass into source categories. It was applied to 156 aerosol samples collected in dichotomous samplers at three sites in the Philadelphia area and analyzed by X-ray fluorescence, instrumental neutron activation, ion chromatography, and pyrolysis. The largest component accounted for 49-55% of the mass of 110 hm diameter particles and consisted of sulfate plus related ions and water. Other components were crustal matter (17-24% of the mass) and vehicle exhaust (4-6% of the mass). Less than 5% of the mass was attributed to primary emissions from five types of stationary sources. Wind-stratified data indicated that 80 f 20% of the sulfate was from a regional background. Multiple linear regression attributed 72 f 8 and 16 f 5 % of S to coal- and oil-fired power plants, respectively. Introduction

Receptor models are used to resolve the composition of atmospheric aerosol into components related to emission sources (1-3). When the chemical mass balance (CMB) receptor model is applied to element concentrations measured by X-ray fluorescence (XRF), four to eight components can typically be resolved on the basis of known chemical signatures (4). A difficulty is that the required signatures are not accurately known for two major components: sulfate and vehicle exhaust. For the former, there is an uncertain amount of water associated with sulfate in particles. For vehicle exhaust, the Pb abundance is difficult to specify in the U.S. because measurements are sparse, and the P b content in gasoline has been declining rapidly during recent years. Multiple linear regression (MLR) has been used to determine the P b abundance when Pb is a unique tracer for vehicle exhaust, but as this report demonstrates, motor vehicles are not the only significant source of Pb. We explore the feasibility of overcoming such problems by using a composite receptor method (combined use of ~~

~

t Present address: Nuclear Reactor Laboratory, Massachusetts

Institute of Technology, Cambridge, MA 02139. t Present address: International Business Machines Corp., Dallas, TX 75234. 46

Environ. Sci. Technol., Vol. 22, No. 1, 1988

several receptor models). I t was tested with data from a field study designed according to recommendations from the Quail Roost I1 Conference ( 5 ) and conducted as part of a larger study to evaluate dispersion models (6, 7). Ambient aerosol was collected in the PM-10 size range (particle diameter 110 pm) at three sites in the Philadelphia area during summer 1982. Source emissions were collected by a dilution-cooling technique at two oil-fired power plants, a coal-fired power plant, a municipal incinerator, an Sb ore roaster, a fluidized catalytic cracker at a refinery, and a secondary Al smelter (8). Surface soil and dust were collected at 30 sites and suspended by an aerosol generator (9). Ambient, source, and soil samples were collected by dichotomous samplers and analyzed by XRF, instrumental neutron activation analysis (INAA), ion chromatography (IC), and pyrolysis with the exception that INAA was not applied to the soil samples. Here we report the ambient aerosol measurements and illustrate the precision and accuracy of concentrations by comparing results of different analytical methods. We present a mass apportionment based on the following steps: (a) Wind-trajectory analysis (IO) was used to identify sources to include in CMB calculations. (b) A new composite method described below used a preliminary CMB to derive a set of adjusted Pb and S concentrations that were then used in MLR to determine abundances of Pb in vehicle exhaust and S in the sulfate component. (c) Final CMBs, based on results of the composite method, were used to apportion mass into nine components. (d) Wind direction stratification was used to detect the relative influences of local and regional sources. (e) MLR of S vs Se and V was used to estimate the particulate S contributions from coal and oil burning. Measurements

Aerosol samples were collected nearly continuously at the three sites shown in Figure 1 for 12-h periods during the day (0600-1800 EDT) and the night (1800-0600 EDT) between July 14 and August 13, 1982. Site 28, at the Institute for Medical Research in Camden, NJ, was in an industrial, commercial area within 10 km of several large emission sources (Figure 2) and was within 400-500 m of several major roads. Site 12, at Northeast Airport, was in a residential area of Philadelphia with isolated light in-

0013-936X/88/0922-0046$01.50/0

0 1987 American Chemical Society

Table I. Comparison of XRF, INAA, and IC Results for 50 Paired Fine-Particle Samples from Camden, NJ (Site 28), between July 14 and August 13, 1982" XRF, ng/m3 mean 6 S

S K Ca

v

Mn Fe Zn Se Br Sb

4060 4200 101 40 19 6 91 82 1.2 29 73

20 20 3 5 4 2.3 3 1.5 0.6 0.8 5

method

other results, ng/m3 mean

IC INAA INAA INAA INAA INAA INAA INAA INAA INAA INAA

3720 3860 144 49 13 6 94 92 1.8 23 79

6

ratio of means (XRF/other)

R

70 900 12 18 0.6 0.3 10 5 0.1 0.3 4

1.09 f 0.09 1.09 f 0.14 0.70 f 0.10 0.81 f 0.11 1.43 f 0.18 1.09 i 0.15 0.97 0.12 0.89 f 0.11 0.67 f 0.10 1.27 f 0.16 0.93 f 0.11

0.97 0.92 0.94 0.65 0.86 0.72 0.89 0.997 0.70 0.97 0.998

*

" R is the correlation coefficient, 6 is the typical amount of random error in individual measurements having concentrations similar to the mean. Uncertainties in the ratios include random error shown above and systematic error discussed in the text.

Figure 2. Map showing sampling site locations and point sources having partlcle emisslon rates above 50 Mg/y.

Figure 1. Map showing locations of sampling sltes 12, 28, and 32. The diagonally shaded regions indicate urban areas, not politlcal boundarles.

dustrial parks; the closest major road was 500 m to the south. Site 34, at Shady Lane Rest Home near Clarksboro, NJ, was in a rural area 1km northwest of the New Jersey Turnpike. Emission sources in the area are described by Core et al. (11). Automated dichotomous samplers (Beckman Instruments) were used to collect fine (C2.5 pm aerodynamic diameter) and coarse (2.5-10 pm) particles on 2 Mm pore size Teflon filters at all three sites. Dichotomous samplers were also used to collect particles on quartz filters (Type 2500 QAST quartz, Palflex Corp.) at sites 12 and 28. Efficiencies for 0.035-1-pm particles were >99.9% for Teflon and 291% for quartz (12). To improve adhesion, the Teflon filters used to collect coarse particles were coated with 25 pg/cm2 of mineral oil before determining tare masses (13). The inlets were prototypes of a PM-10 inlet now available from Sierra-Andersen, Inc. Flow rates, set at 1 ms/h, were measured every 5 d in a dry-gas test meter and were constant within 4%. A t the end of the study, flow rates were checked by an auditor; deviations ranged from 0 to 12%, and the average was 5 % , Teflon filters were analyzed for mass by &ray attenuation (14,15)in a RH = 50% laboratory atmosphere and for elemental composition by an energy-dispersive XRF

spectrometer having Ti, Mo, and Sm secondary targets (16, 17). Fine-fraction filters were sent to the University of Maryland for analysis by INAA at the National Bureau of Standards' heavy water reactor (8). Pyrolysis of 0.35cm2portions of quartz filters was used to determine volatilizable carbon (V-C) (650 "C in a He atmosphere) and nonvolatilizable carbon (NV-C) (850 "C in a 98% He, 2% O2atmosphere) (18). The remainder of each quartz filter was analyzed for sulfate and nitrate by IC and for ammonium by colorimetry (16).

Results and Discussion Precision and Accuracy. Systematic errors were f 7 % for sulfate by IC, i l l %for AI by XRF, and f7% for other elements by XRF. Errors for INAA were the larger of either f10% or random error determined from counting statistics. Table I lists typical values of random error 6. Table I also shows correlation coefficients and a comparison of mean values for species with mean concentration above 6. For such species, the paired data are highly correlated. The ratios of means agree within overall errors for S, Mn, Fe, Zn, and Sb. For each species measured at site 28, Table I1 lists average concentration, average uncertainty, and the number of samples having concentration above twice the uncertainty. Variability in the blanks caused the uncertainty for V-C to be large. The data in Tables I and I1 are based on the 50 sampling periods at site 28 for which we had complete data from all measuring methods. Ionic Composition. Table I shows that the mean XRF and IC data for fine-particle S agree within measurement Environ. Sci. Technol., Vol. 22, No. 1, 1988 47

Table 11. Aerosol Composition at Site 28 in Camden, NJ, during Summer 1982"-

mass NOc S042"4'

v-c

NV-C Na

A1 Si

S c1

K Ca sc* Ti V Cr Mn

Fe co* Ni Zn Ga* As* Se

Br Sr Mo* Ag* Cd In* Sn Sb I* cs* La* Ce* Sm*

W* Au* Pb

method

N

P-gauge IC IC color. pyrol. pyrol. INAA d XRF XRF XRF XRF XRF INAA XRF d d d XRF INAA XRF XRF INAA INAA d XRF XRF INAA INAA d INAA XRF d INAA INAA INAA INAA INAA INAA INAA XRF

49 3 50 49 25 50 50 50 50 50 3 49 50 50 19 50 49 50 50 50 46 50 16 49 50 50 10 38 18 24 12 9 50 46 23 50 45 50 34 27 50

fine fraction av 28700 (3100) 130 (160) 11200 (860) 3600 (270) 2050 (1010) 1870 (140) 146 (15) 53 (6) 103 (21) 4200 (290) 3 (5) 101 (8) 40 (5) 14 (2) 15 (9) 13 (1.4) 1.5 (0.2) 6 (0.7) 91 (7) 480 (60) 11 (1.5) 82 (6) 76 (84) 630 (220) 1.8 (0.2) 29 (2) 0.4 (0.6) 880 (360) 167 (120) 2.2 (0.7) 7 (4) 5 (4) 79 (8) 1040 (320) 23 (14) 1120 (130) 610 (100) 40 (5) 230 (60) 1.7 (0.9) 249 (15)

coarse fraction av

N

43 37 23 0 1 40

11400 (2800) 570 (170) 520 (300) -270 (90) 620 (1000) 420 (60)

49 50 50 41 50 50

550 (170) 1610 (390) 230 (140) 69 (13) 151 (23) 360 (40)

36 25 13 44 50

65 (12) 7 (4) 3 (3) 11 (3) 490 (40)

33 47

4 (1) 30 (4)

2 50 39

0.0 (0.5) 15 (1.4) 2 (0.6)

1

0 (2)

3 28

1 (3) 181 (13)

50

54 (5)

50 samples, N is the number having concentrations above 2 Data in parentheses represent mean uncertainties. bAn asterisk (*) denotes data in pg/m3; all other data are in ng/m3. cV-C and NV-C pertain to volatilizable and nonvolatilizable carbon, respectively. dThe method was INAA for fine and XRF for coarse. a For

u.

error. Because IC detected only sulfate, we conclude that within measurement error, all S occurred as sulfate in the fine fraction. Ammonium and sulfate were highly correlated (R = 0.97). The NH,+/SO?- molar ratios were 1.51 f 0.11 and 1.72 i 0.12 for sites 12 and 28, respectively. Data in Table I1 indicate that any Na, K, Ca, Fe, and Pb cations would contribute <8% of the anion to sulfate molar ratio. We assume that the remaining amount of anion was balanced by H+ and deduce a H+/SO?- molar ratio of 0.4 f 0.2. Such a value is a lower limit for H+because we did not protect samples from neutralization by NH, during 1-14 d of storage in dichotomous samplers. Table I1 indicates a significant negative bias for coarse-particle ammonium, which we explain as follows: the dichotomous sampler deposits 10% of the fine particles on the coarse-fraction filter where (NH&S04 in fine particles may contact alkaline coarse particles, causing the former to decompose and lose NH,. When computing species concentrations, we made a mathematical correction for fine particles deposited on the coarse-fractionfilter (161, assuming zero loss; thus, any loss would cause negative bias. 48

Environ. Sci. Technol., Vol. 22, No. 1, 1988

Nitrate data reported here pertain to nonvolatilized nitrate. Ammonium nitrate is unstable, and the more stable alkaline nitrate compounds may decompose upon contact with acidic fine particles after collection on a filter. Thus, little nitrate was detected in the fine fraction. Most nitrate was collected in the coarse fraction where Ca, a substance often in alkaline form, is abundant and can react with gaseous HNO, to form stable Ca(NO3)> Little nitrate was detected in source (8) or soil (9) samples, which suggests that coarse-particle nitrate was produced by reactions in the atmosphere. Wind-Trajectory Method To Identify Sources To Include in CMB. Following Rheingrover and Gordon (IO),we used hourly data on surface winds at Philadelphia International Airport to compute resultant wind direction 8 and standard deviation 60 for each 12-h period. Also, t,he mean concentration E and standard deviation s were calculated for each species. The wind-trajectory method selected events having 68 120' and x 232 + 2s. The wind direction criterion was satisfied for about 18 of the 12-h periods, and both criteria were satisfied for one or two periods, depending on the species. For periods satisfying both criteria, emission sources were identified when element abundance ratios matched those in source signatures (8,191. The wind-trajectory method selected two consecutive periods on July 21-22 with 8 = 318'. Then Na, K, Zn, Cd, Sn, and Pb in fine particles at site 28 were at maxima, and element abundance ratios matched within 2a those measured at the incinerator 15 km northwest of site 28 (8). (Here u includes uncertainty in both source and ambient data.) Another incinerator 4 km northwest of site 28 (Figure 2) could have been a major contributor. Nitrate and C1 also had maxima during the event, but ambient C1 was very deficient and NO3- was enriched relative to incinerator emissions (8). We attribute the C1 loss and NO< gain to reactions of NaCl and KCI in incinerator particles with atmospheric HNO, vapor and H2S04particles. Similar C1 loss was observed in St. Louis (IO)and Washington, DC (20). The wind-trajectory method selected other events with elevated Ti and Sb concentrations and indicated a paint pigment plant and an Sb roaster, both 6 km south-southwest of site 28 (Figure 2). On the night of July 18-19, 8 = 237' and Sb concentrations reached maxima of 1.1and 2.7 pg/m3 for the fine and coarse fractions, respectively. Also selected were events with elevated V, Ni, and Mo concentrations in ratios within 2a of emissions from oil burning. Other events had elevated La, Ce, and Sm concentrations with ratios that matched catalytic cracker emissions (8) within a factor of 2. Several such sources were in the area, but specific ones were not identified. Catalytic cracker emissions were detected only in fine particles because the INAA method, needed to detect tracer elements La, Ce, and Sm, was not applied to ambient coarse particles. However, emissions measured at a catalytic cracker had no significant coarse fraction (8). Time-series plots of coarse particle C1 in Figure 3 show maxima at three sites between August 6 and August 8 (Julian days 218-220). During December 1980, Shaw et al. (21) detected the simultaneous occurrence of high C1 concentrations in fine particles in several midwestern states and attributed the event to an intrusion of marine air from the Pacific Ocean. We attribute the event in Philadelphia to marine aerosol from the Atlantic Ocean because the elevated C1 concentrations were mainly in the coarse fraction and because the surface winds on August 6 in Philadelphia, Wilmington, Atlantic City, and Newark were

utilities (8),an Sb roaster (8), paint pigment manufacturing (24),and local dust (9). Using these 13 elements and 6 source signatures, we applied the CMB model to fineparticle data for each 12-h period at all sites to obtain 156 sets of M,. Then, we calculated 0,' =

Oi - CAIJMj

(3)

where Oi'represents M', [S'], and [Pb'], which are the portions of observed mass, S, and P b concentrations due only to the vehicle exhaust and sulfate components. We applied a statistical package for MLR (25) to all 156 fine-fraction observations and obtained M' = 3546 f 774 ng/m3

+ (4.91 f 0.13)[S'] + (14.5 f 3.2)[Pb'] (4)

-

g 0.8

-

SITE 34

0 c

2 0.4 LL IY

KIY O 4

8

195

200

205 210 JULIAN DAY

215

220

225

Flgure 3. Coarse-particle CI, fine-fraction S, and 12-h wind resultants between July 14 and August 13, 1982. One, two, three, and four barbs on the wind vectors indicate speeds of 0-5, 5.1-10, 10.1-15, and >15 km/h, respectively. Darts point in direction of airflow.

easterly. Thus, we included a marine component in our coarse-particle CMB. Composite of CMB and MLR. In a study in Denver during the winter, Lewis et al. (22)used MLR to determine abundances of elements in vehicle exhaust, wood smoke, sulfate, and crustal matter. Because atmospheric K, their tracer for wood smoke, included a contribution from soil, they used the measured K concentration minus a correction for soil as a wood-smoke tracer. We could not use the algebraic method of Lewis et al. to derive a P b tracer for vehicle exhaust because there were multiple sources of Pb, which themselves lacked unique tracers. Rather, we used CMB to determine nonvehicular Pb, which we subtracted from the measured P b concentration to yield a tracer for vehicle exhaust. Our composite of CMB and MLR is outlined below. The CMB method expresses the concentration C, of species i as

C, = CALjMj J

(1)

where A , is the abundance of species i in component j and M, is the total mass concentration for component j . Using data on C, and A,, unknown values MJ are found by a least-squares method that minimizes the expression 'X = C(C,- 0 J 2 / E 1 2

(2)

where Oi is the observed concentration of species i, and E? is the effective variance, which includes the uncertainties in 0, and A, (23). Two criteria must Le met for each species i in eq 2: (a) its abundance in each component must be known, and (b) all its major sources j must be included in eq 1. For our data these criteria could be met for a fine-particle CMB based on Al, Si, Ca, Ti, V, Ni, Zn, Cd, Sn, Sb, La, Ce, and Sm in the following six components: municipal incinerators (8),catalytic crackers (8), oil combustion by electric

and the multiple correlation was R = 0.95. We interpret the reciprocal of the regression coefficient of [S'] in eq 4 as the abundance of S in the regional sulfate component, 20.4 f 1.4%. The uncertainty includes the standard error in eq 4 and the systematic measurement error for S. Such an abundance is lower than the values 24.2 and 26.1% for S in pure (NH4)zS04and NH4HS04, respectively. Sulfur abundances ranging from 12 to 20% were obtained by other investigators, who applied MLR and multivariate methods to aerosol data (22, 24, 26). Water and possibly organic matter retained on acidic sulfate particles during laboratory mass analysis may account for S abundances lower than 24.2%. Likewise, eq 4 indicates a 6.9 f 1.6% abundance of P b in vehicle exhaust. This falls within the range of results obtained by other investigators: 7.0% for a Pennsylvania Turnpike tunnel during 1977 (27), 7.2 f 0.2% for Watertown, MA, during 1979-1981 (26),7.3% for Detroit during July 1981 (28),and 4.4 f 0.6% for Denver during winter 1982 (22). The intercept in eq 4, which is comparable to the uncertainty of each mass measurement, may result from mass measurement error or may represent sources not included in the CMB. Mass Apportionment. Fine-particle mass was apportioned by CMB into eight components and shown in Table 111. Vehicle exhaust and sulfate were included with the six components used in the preliminary CMB. For vehicle exhaust, the P b abundance of 6.9 f 1.6% was derived from eq 4. Abundances of other elements in vehicle exhaust (S, Cr, Mn, Fe, Ni, and Br) were taken from Pennsylvania Turnpike tunnel data (27)adjusted for the vehicle mix in Philadelphia (94% gasoline, 6% diesel from ref 11). The sulfate component included the 20.4 f 1.4% S abundance derived from eq 4. Concentrations of other elements were from the regional sulfate signature of ref 29 normalized to our S value. The uncertainties in the derived mass components were obtained when x2 was minimized (23). Except for C1, Cr, Se, and I, the measured and calculated element concentrations agree within f2E1, where E: is the effective variance defined above. Calculated C1 and Br values are too large because our model does not account for volatilization. The regional sulfate component represents most of the calculated Se, but that signature, derived with principal components analysis (26, 30) from Shenandoah Valley data (291,does not exactly represent Se in Philadelphia. Most of the measured I is not explained. Deviations for such elements have little effect on our mass apportionment. We applied CMB as in Table I11 to each sample; averages for each site are shown in Table IV. The indicated standard errors were obtained by compounding individual error estimates, assuming that they were independent. Environ. Sci. Technoi., Vol. 22, No. 1, 1988

49

Table 111. CMB Results for Average Fine-Particle Composition at Camden, NJ (Site 28), between J u l y 14 and August 13, 1982n*b

v-c NV-C Na Al' Si' S' c1 K Ca' Ti' V' Cr Mn Fe co* Ni' Zn' As* Se* Br Mo* Ag* Cd' In* Sn' Sb' I* cs* La*,' Ce*sc Sm*+ W* Pb' mass Gmass

calcd

measd

crustal

oil

1008 f 1121 1122 f 568 103 f 36 39 f 12 136 f 37 4 196 f 403 223 f 33 64 f 19 35 f 9 18 f 9 11 f 3 l f 0 5 f l 76 f 22 706 f 147 13 f 3 82 f 8 213 f 219 887 f 233 70 f 34 666 f 400 50 f 100 I f 1 9f4 6f4 79 f 9 104 f 304 9 f 15 904 f 192 746 f 177 49 f 13 51 f 119 249 f 45 24853 f 3421 2 124

2 046 1867 146 53 103 4 196 3 101 40 15 13 2 6 91 483

76

16 29 21 5 17 89 0

11

82 632 1800 29 900 200 2

7 5 79 1000 23 1120 609 40 200 249 28 282 3 124

11

21 16 63 1 0 6 9 3 0 0 1

45 17 0 0 4 0 0 11 0 0 0 0 0

0 5 13 34 5 51 2 742 357

1

20 1 11

0 0 11 684 13 7 31 15 0 381 0 0 0 0 0 0 0 200 155 8 0 10 740 131

paint Pig.

0 0 0 2 0

0 0 2 4 14 0 0 0 10 0 0 0 0 0 1 0 0 0 0 0 0

cat. crack 1 0 1

14 45 28 0 0 0 1 0 0 0 0 3 0 0 0 2 0

0 0 0 0

0 0 0 0 0 0 0 0 690 557 36 0 0

62 41

223 43

0

0 0

munic incin

veh exh

4 25 45 2 12 21 194 55 2 0 0 0 0 2 2 0 71 47 29 2 274 50

911 1057 16 0 0 46 29 0 0 0 0 0 2 7 0 0 3 0 0 68 0 0 0 0

1 0 0 0 0

0 0 0 0 0

1

4 010 0 0

0 0 0 0 0 0 0 0 0

0 0 0 0 2 0 0 0 1

0

104 0 0

132 841 0 0 0 0 6 0 0 0 0 0

0

0

0

0 0 180 2 603 667

0 0 0

0 0 14

105 12

19658 1978

1

0 0

1 0

4

720 82

S

0 0 0 0 0 0 0 0 1 77 0 0 0

4 5

1 0 0 0 42

Sb roast.

nAn asterisk (*) denotes data in pg/m3; all other data are in ng/m3. bCalculated species uncertainty Eiis square root of effective variance. Elements included in least-squares fit.

Also indicated are estimates of overall uncertainty due to uncertainty in abundances of key elements in source signatures. The component labeled "other" is the intercept in eq 4 and represents bias or components not included in the CMB. Results for the dust signature are labeled "crustal matter" and represent a broad category that includes minerals and coal fly ash. The coarse fraction results in Table IV are based on CMB with five components: municipal incinerators (81, an Sb ore roaster (a), surface dust (9),sulfate, and marine aerosol. Elements used in the least-squares fit were Al, Si, S, C1, Ti, Mn, Zn, Cd, Sn, and Pb. Because ammonium was not present in the coarse fraction (Table 111,we used the 33% abundance of S in sulfate for the coarse sulfate component. The marine signature was from ref 19; the C1 abundance was 40%, which is lower than that of dried seawater and represents some loss of Cl. A large uncertainty is shown for the marine component because it was determined almost exclusively by C1, a volatilizable element. Because we did not constrain our CMB solutions to positive values, negative values below the detection limit were sometimes obtained, as coarse-particle results in Table IV indicate. Estimating Local and Regional Components. Two facts suggest that the sulfate component, which accounts for 50-55% of PM-10, is not of local origin: (a) Paired S data for site 12 vs site 28 and site 28 vs site 34 were highly correlated ( R = 0.93). (b) Time-series plots in Figure 3 show that fine-particle S has similar concentrations at all three sites. 50

Environ. Sci. Technol., Vol. 22, No. 1, 1988

Table IV. Average Mass Balance in ng/m3 for July 14 to August 13, 1982, Deduced by Composite of CMB and MLR Methods site component

12

fine fraction crustal matter oil fly ash Ti-rich paint pigment fluidized catalyst cracker municipal incinerators antimony roaster motor vehicle exhaust sulfate, cations and water other (MLR intercept) calculated total measured total coarse fraction crustal matter marine sulfate municipal incinerators antimony roaster calculated total measured total PM-10 (fine + coarse) calcuiated total measured total '

site 28

site 34

870 f 60 690 1240 440 480 690 f 20 53 f 6 7 29 195 k 9 93 140 190 550 700 f 20 2 94 f 3 5 2 280 2630 f 120 1470 18600 19400 f 320 18500 3 550 3 550 f 770 3 550 27 000 28000 f 850 25 000 27 000 28300 f 440 26 000

overall uncertainty, % 50 30 30

30 30 10 20 10 10 10

5 200 105 720 -17 8 5 900 7 900

30

34000 38000 f 900 31000 34900 39700 f 600 33900

10 10

6 500 8700 f 210 210 f 30 150 590 h 70 450 44 f 29 100 230 f 14 15 7 200 9800 f 230 7 900 11400 f 400

50 30 30

10 20 10

To estimate contributions from regional sources, we selected cases when wind direction was steady along the 30-210' line of our samplers (Figure 2). Paired samples at sites 12 and 34 were selected on the basis of having at

Table V. Ratios of Mean Concentrations at Sites 12 and 34 during Steady Winds from SSW and NNE between July 14 and August 13, 1982“

species regional I-F Se-F S-F mixed Ce-F Na-F Al-F Si-F K-F V-F Si-C AS-F Fe-F A1-C Br-F Fe-C Pb-F Ca-F Cr-F Ca-C Br-C Pb-C La-F MO-F Mn-F local Ni-F Ni-C CO-F Zn-F Zn-C Sb-F Sb-C

wind from SSW, site 34/site 12 ( N = 11)

wind from NNE, site l2/site 34 (N = 5 )

1.22 f 0.32 0.85 f 0.17 0.82 f 0.22

0.78 f 0.15 0.86 f 0.19 0.78 f 0.13

0.73 f 0.25 0.71 f 0.18 0.70 f 0.25 0.61 f 0.26 0.60 i 0.21 0.58 f 0.13 0.54 f 0.17 0.52 f 0.18 0.47 f 0.17 0.45 f 0.16 0.45 f 0.06 0.38 f 0.13 0.38 f 0.06 0.35 f 0.15 0.33 f 0.09 0.29 f 0.13 0.27 f 0.05 0.26 f 0.05 0.25 f 0.08 0.25 f 0.12 0.23 f 0.06

0.40 f 0.11 0.51 i 0.16 0.80 f 0.22 0.94 f 0.24 0.69 f 0.22 0.47 f 0.10 0.65 f 0.23 0.92 f 0.44 0.76 i 0.17 0.89 f 0.25 0.92 i 0.28 0.62 f 0.18 0.74 f 0.23 0.84 i 0.19 0.89 i 0.17 0.67 f 0.23 0.66 f 0.23 0.61 f 0.23 0.13 f 0.05 0.68 i 0.20 0.62 f 0.15

0.20 f 0.07 0.16 f 0.09 0.14 f 0.05 0.11 f 0.04 0.03 f 0.02 0.04 f 0.04 0.00 f 0.03

0.45 f 0.12 0.06 i 0.09 0.40 i 0 . 1 2 1.40 i 0.50 0.72 f 0.12 0.07 f 0.03 0.06 i 0.14

‘The classification pertains only to winds from SSW as discussed in the text. F denotes fine and C denotes coarse.

least 75% of the hourly surface wind directions recorded at Philadelphia International Airport in the SSW or NNE quadrant. Table V shows ratios of mean species concentrations for steady wind from NNE (345-75’) and SSW (165-255O) quadrants. The data are sorted according to decreasing values of the ratio site 34/site 12 for winds from SSW, and the sources are labeled “local”, “mixed”, and “regional” according to the ranges 0-0.2,0.2-0.8, and 0.8-1. The rationale for this classification is that site 34 is moderately free of upwind urban areas during winds from SSW (see Figure 1). Thus, a ratio -0 implies local sources, and a ratio N 1implies regional sources. The classification in Table V does not apply to winds from NNE because Figure 1 shows large urban areas NNE of site 12. Emissions from the nearby New Jersey Turnpike SSW of site 34 cause P b and Br to be classified as mixed. Table V shows that local sources contribute 95 f 5 % of the Sb, whereas regional sources contribute 80 f 18% of the S and 85 f 18% of the Se. Altshuller (31) deduced local and regional components for sulfate measured at 45 stations in eastern U.S. between 1963 and 1978. Early in that period, local sources contributed -45% of total sulfate during summer months. By 1978 the local component had decreased to -25% due to controls on S emissions applied mainly in urban areas (31). The regional nature of particulate S in Philadelphia is further indicated in Table I1 by the average S concentrations being within 20% of summertime values at Great Smoky Mountains National Park (32),Shenandoah Valley (32),Ohio River

Table VI. Apportionment of Sulfur in Fine Particles by MLR and Total Sulfur Dioxide Emission Rates by Category for Various States

method

sulfur from each source,

so2

%

emissions,O G4Y

other

fine-particle MLR S vs Se and V S vs Se and Ni SO2 emissions from Ohio Indiana Pennsylvania West Virginia Kentucky New York North Carolina Maryland New Jersey Virginia Delaware

coal

1Of9 7 3 i 8 14i9 71i8 4 3 10 4 5 10 10 13 34 16 8

95 93 85 95 95 40 80 71 27 53 42

oil 17f5 15f4 1

4 5 1 0 50 10 16 39 31 50

2813 2076 2011 1205 1184 934 583 359 329 313 101

nData on SOz emission rates during 1980 are from ref 36.

Valley (33),Newark, NJ (34),Detroit (28),and St. Louis, MO (35),between 1976 and 1981. Sources of Particulate Sulfur. An emission inventory summarized in Table VI shows that about 90% of the SOz,the precursor for particulate S, is emitted from coaland oil-fired power plants (36). Investigators have attributed the S and Se at Shenandoah Valley, VA, to coal-fired power plants (29,32). In coastal states, power plants burning oil are major sources of S (36),V, and Ni. Assuming that Se and either V or Ni are tracers for coaland oil-fired power plants, respectively, we used MLR to express fine-particle S as

[SI = 380 f 355 ng/m3

+

(1791 f 201)[Se] + (67 f 21)[V] (5)

[SI = 555 f 342 ng/m3 + (1740 f 204)[Se] + (74 f 22)[Ni] (6) Residuals were approximately normally distributed, and multiple correlations were R = 0.67 for 156 samples. Because S is emitted mainly as SOz, atmospheric reactions are required to produce particulate S. Therefore, the regression coefficients in eq 5 and 6 represent averages of time-dependent quantities. Variability in the fraction of SOz converted to SO-: could account for correlations that are only moderately high. Table VI shows apportionments of S on the basis of the mean of each term in eq 5 and 6 divided by the mean fine-particleS concentration. Table VI also shows amounts of SOzemitted by coal- and oil-fired power plants in several states (36). The regression results indicate that coal- and oil-fired power plants contribute 72 f 8% and 16 f 5%, respectively, to particulate S. Such a result for coal is similar to the 80-95% range of values shown in Table VI for states that are high S emitters south and west of our sampling area. Summary A new composite receptor method that combines wind-trajectory analysis, CMB, and MLR was applied to data obtained by XRF and INAA. The combined use of XRF and INAA enabled more sources to be resolved than was possible when only one method was used. The former provided essential data on Si, S, Ni, and Pb; the latter provided essential data on Al, V, Se, La, Cs, and Sm. Although INAA was applied only to samples in the fine Environ. Scl. Technol., Vol. 22, No. 1, 1988

51

fraction, coarse-particle INAA data for Na would have been helpful for improving the accuracy of the marine component. The wind-trajectory method identified five categories of stationary sources to include in the CMB. Perhaps more sources could have been identified if the sampling periods had been shorter than 12 h. The composite method provided an estimate of the average P b abundance in vehicle exhaust when incinerators and oil combustion contributed a portion of the Pb. Final CMB results indicate that the vehicle exhaust portion of PM-10 ranged from 4 to 6%. Stationary sources included in our CMB contributed less than 5% to PM-10. The sulfate component contributed 49-54% of PM-10 and consisted of sulfate plus related water and ions. Windstratified data indicated that 80 f 20% of particulate S was from regional sources. Multiple linear regression of S vs tracers Se and either V or Ni attributed 72 f 8 and 16 f 5% of particulate S to coal- and oil-fired power plants, respectively. Interpretations reported here are a few of the possibilities that we expect other investigators may attempt. Any investigator may obtain our data and source signatures on IBM-PC readable disks by sending a pair of 360-Kbyte diskettes or a single 1.2-Mbyte diskette to the corresponding author. Acknowledgments

We thank George Russwurm, William Ellenson, Charles Tipton, Carolyn Owen, Chris Pressley, Mark Mason, Margaret Beaman, James Godowitch, and the NBS reactor staff for technical assistance. Registry No. C, 7440-44-0; NH4+,14798-03-9;Na, 7440-23-5; AI, 7429-90-5; Si, 7440-21-3; S, 7704-34-9; C1, 7782-50-5; K, 7440-09-7; Ca, 7440-70-2; Sc, 7440-20-2; Ti, 7440-32-6; V, 7440-62-2; Cr, 7440-47-3; Mn, 7439-96-5; Fe, 7439-89-6; Co, 7440-48-4; Ni, 7440-02-0; Zn, 7440-66-6; Ga, 7440-55-3; As, 7440-38-2; Se, 7782-49-2; Br, 7726-95-6; Sr, 7440-24-6; Mo, 7439-98-7; Ag, 7440-22-4; Cd, 7440-43-9; In, 7440-74-6; Sn, 7440-31-5; Sb, 7440-36-0; I, 7553-56-2; Cs, 7440-46-2; La, 7439-91-0; Ce, 7440-45-1; Sm, 7440-19-9; W, 7440-33-7; Au, 7440-57-5; Pb, 7439-92-1.

Literature Cited (1) Receptor Methods for Source Apportionment; Pace, T. G., Ed.; Air Pollution Control Association: Pittsburgh, PA, 1986. (2) Stevens, R. K.; Pace, T. G. Atmos. Environ. 1984,18,1499. (3) Hopke, P. K. Receptor Modeling in Environmental Chemistry; Wiley: New York, 1985. (4) Henry, R. C. In Receptor Models Applied to Contemporary Pollution Problems; Air Pollution Control Association: Pittsburgh, PA, 1982; pp 141-162, SP-48. (5) Gordon, G. E.;Pierson, W. R.; Daisey, J. M.; Lioy, P. J.; Cooper, J. A.; Watson, J. G.; Cass, G. R. Atmos. Environ. 1984, 18, 1567. (6) Ku, J. Y.; Rao, K. S. Evaluation of the PEM-2 Using the 1982 Philadelphia Aerosol Field Study Data Base;National Technical Information Service: Springfield, VA, April 1986; EPA-600/3-86-016, NTIS PB86-167 921/AS. (7) Batterman, S. A. Ph.D. Dissertation, Massachusetts Institute of Technology, Cambridge MA, 1986. (8) Olmez, I.; Sheffield, A. E.; Gordon, G. E.; Houck, J. E.; Pritchett, L. C.; Cooper, J. A,; Dzubay, T. G.; Bennett, R. L. submitted for publication in J. Air Pollut. Control Assoc. (9) Batterman, S. A.; Dzubay, T. G.; Baumgardner, R. E. submitted for publication in Atmos. Environ. (10) Rheingrover, S. W.; Gordon, G. E. Aerosol Sci. Technol., in press.

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(11) Core, J. E. “Philadelphia Airshed Aerosol Study Summer, 1982 Sampling Site Characterization and Source Inventory Survey”; NEA, Inc.: Beaverton, OR, 1982. (12) Liu, B. Y. H.; Pui, D. Y. H.; Rubow, K. L. In Aerosols in the Mining and Industrial Work Environments; Marple, V. A., Liu, B. Y. H., Eds.; Ann Arbor Science: Ann Arbor, MI, 1983; Vol. 3, pp 989-1938. (13) Dzubay, T. G.; Barbour, R. K. J. Air Pollut. Control Assoc. 1983, 33, 692. (14) Jaklevic, J. M.; Gatti, R. C.; Goulding, F. S.; Loo, B. W. Environ. Sci. Technol. 1981, 15 680. (15) Courtney, W. J.; Shaw, R. W.; Dzubay, T. G. Environ. Sci. Technol. 1982,16, 236. (16) Dzubay, T. G.; Stevens, R. K.; Lewis, C. W.; Hern, D. H.; Courtney, W. J.; Tesch, J. W.; Mason, M. A. Environ. Sci. Technol. 1982, 16, 514. (17) Jaklevic, J. M.; Gatti, R. C.; Goulding, F. S.; Loo, B. W.; Thompson, A. C. Aerosol Analysis for the Regional Air Pollution Study; National Technical Information Service: Springfield, VA, March 1981; EPA-600/4-81-006, NTIS PB81-157 141. (18) Stevens, R. K. Environ. Znt. 1985, 11, 271. (19) Core, J. E.; Shah, J. J.; Cooper, J. A. Receptor Model Source Composition Library; Office of Air Quality Planning and Standards, U.S. E P A Research Triangle Park, NC, Nov 1984; EPA-450/4-85-002. (20) Kowalczyk, G. S.; Choquette, C. E.; Gordon, G. E. Atmos. Environ. 1978, 12, 1143. (21) Shaw, R. W.; Binkowski, F. S.; Courtney, W. J. Nature (London) 1982,296, 229. (22) Lewis, C. W.; Baumgardner, R. E.; Stevens, R. K.; Russwurm, G. M. Environ. Sci. Technol. 1986, 20, 1126. (23) Watson, J. G.; Cooper, J. A.; Huntzicker, J. J. Atmos. Environ. 1984, 18, 1347. (24) Chang, S. N.; Hopke, P. K.; Gordon, G. E.; Rheingrover, S. W. Aerosol Sci. Technol., in press. (25) Dixon, W. J. BMDP Statistical Soytware; University of California Press: Berkeley, CA, 1983. (26) Thurston, G. D.; Spengler, J. D. Atmos. Environ. 1985,19, 9. (27) Pierson, W. R.; Brachaczek, W. W. Aerosol Sci. Technol. 1983, 2, 1. (28) Wolff, G. T.; Korsog, P. E. Atmos. Environ. 1985,19,1399. (29) Tuncel, S. G.; Olmez, I.; Parrington, J. R.; Gordon, G. E.; Stevens, R. K. Environ. Sci. Technol. 1985, 19, 529. (30) Lowenthal, D. H.; Rahn, K. A. Atmos. Environ. 1987,21, 257. (31) Altshuller, A. P. Environ. Sci. Technol. 1980, 14, 1337. (32) Stevens, R. K.; Dzubay, T. G.; Lewis, C. W.; Shaw, R. W. Atmos. Environ. 1984, 18, 261. (33) Shaw, R. W.; Paur, R. J. Atmos. Environ. 1983,17, 1431. (34) Lioy, P. J.; Daisey, J. M.; et al. J. Air Pollut. Control Assoc. 1983, 33, 649. (35) Dzubay, T. G. Ann. N.Y. Acad. Sci. 1980,338,126. (36) Gschwandtner, G.; Gschwandtner, K. C.; Eldridge, K. Historic Emissions of Sulfur and Nitrogen Oxides in the United States from 1900 to 1980; U.S.EPA: Research Triangle Park, NC, Nov 1984; Vol. 11, EPA-600/7-85-009b (NTIS PB85-191203/AS, April 1985).

Received for review March 2,1987. Accepted July 29, 1987. The Maryland work was supported by EPA Cooperative Agreement CR806263, and computer time was provided by EPAB National Computer Center and the Maryland Computer Science Center. Although research described in this article has been funded by the U S . Environmental Protection Agency, it has not been subjected to agency review and, therefore, does not necessarily reflect the views of the Agency, and no official endorsement should be inferred. Mention of commercial products does not constitute endorsement by the U.S. EPA.